Organic Letters,
Год журнала:
2023,
Номер
25(40), С. 7440 - 7445
Опубликована: Сен. 29, 2023
Fluoroalkylated
compounds
are
important
entities
in
agrochemicals,
pharmaceuticals,
and
materials.
The
catalytic
dicarbofunctionalization
of
alkenes
represents
a
powerful
strategy
for
the
rapid
construction
diversification
compounds.
In
this
vein,
multicomponent
cross-coupling
reactions
(MC-CCR)
can
provide
an
efficient
synthetic
route
to
build
molecular
complexity.
work,
we
report
first
iron-catalyzed
three-component
fluoroalkylarylation
enamides
via
selective
formation
trapping
α-amide
radicals
under
mild
conditions
fast
reaction
times.
tolerates
variety
commercially
available
aryl
Grignard
reagents
fluoroalkyl
halides.
Finally,
use
removable
phthalimido
group
provides
prepare
highly
valuable
γ-difluoroalkylated
amines.
ACS Catalysis,
Год журнала:
2024,
Номер
14(4), С. 2144 - 2150
Опубликована: Янв. 25, 2024
The
modular
four-component
carbonylation
of
unsaturated
hydrocarbons
represents
an
elegant
strategy
for
the
one-pot
synthesis
complex
carbonyl
compounds.
However,
this
is
currently
focused
on
1,2-difunctionalization
olefins
or
alkynes,
and
1,4-alkylcarbonylation
1,3-enynes
remains
unexplored.
In
study,
we
report
a
Ni-catalyzed
CF3-containing
under
1
atm
CO,
which
affords
tetra-substituted
CF3-allenyl
ketones
with
good
yields
selectivity.
This
protocol
features
mild
conditions,
broad
substrate
scope,
acceptable
functional
group
compatibility.
Control
experiments
revealed
that
reactivity
oxime
esters
(regulated
by
leaving
groups)
polarity
matching
are
crucial
success
cascade.
Preliminary
mechanistic
studies
suggest
acyl
nickel
key
intermediate
in
transformation.
Journal of the American Chemical Society,
Год журнала:
2024,
Номер
146(12), С. 7971 - 7978
Опубликована: Март 14, 2024
We
describe
a
nickel-catalyzed
carbonylative
cross-coupling
of
unactivated
secondary
alkyl
electrophiles
with
the
organozinc
reagent
at
atmospheric
CO
gas,
thus
allowing
expedient
construction
unsymmetric
dialkyl
ketones
broad
functional
group
tolerance.
The
leverage
newly
developed
Chinese Journal of Chemistry,
Год журнала:
2023,
Номер
42(2), С. 177 - 189
Опубликована: Сен. 4, 2023
Comprehensive
Summary
Carbonyl
compounds
have
attracted
considerable
attention
due
to
their
extensive
applications
in
drug
discovery.
Furthermore,
they
are
important
synthetic
intermediates
for
the
construction
of
carbon‐carbon
and
carbon‐heteroatom
bonds.
Transition‐metal‐catalyzed
carbonylation
via
insertion
CO
is
one
most
efficient
straightforward
strategies
access
carbonyl
compounds.
However,
transition‐metal‐catalyzed
carbonylative
reactions
require
expensive
toxic
noble‐metal
catalysts.
Therefore,
there
a
growing
demand
exploration
nickel‐catalyzed
earth
abundance
low
cost
nickel.
Compared
with
well‐established
palladium‐catalyzed
reactions,
analogous
transformations
been
relatively
underdeveloped.
This
primarily
because
strongly
binds
nickel,
often
resulting
catalyst
poisoning.
In
recent
years,
some
research
groups
focused
on
using
surrogates
or
NN
2
pincer
nickel
circumvent
formation
Ni(CO)
4
.
Nickel‐catalyzed
has
applied
carbonyl‐containing
compounds,
such
as
ketones,
carboxylic
acids,
thioesters,
acyl
chloride
carboxamides.
Angewandte Chemie International Edition,
Год журнала:
2024,
Номер
63(25)
Опубликована: Апрель 19, 2024
The
reaction
regioselectivity
of
gem-difluoroalkenes
is
dependent
on
the
intrinsic
polarity.
Thus,
reversal
addition
remains
a
formidable
challenge.
Herein,
we
described
an
unprecedented
hydrogen
atom
transfer
(HAT)
to
triggered
by
Fe-H
species
for
formation
difluoroalkyl
radicals.
Hydrogenation
in
situ
generated
radicals
gave
difluoromethylated
products.
Mechanism
experiments
and
theoretical
studies
revealed
that
kinetic
effect
irreversible
HAT
process
resulted
this
scenario,
leading
less
stable
α-difluoroalkyl
radical
regioisomer.
On
basis
new
gem-difluoroalkene,
iron-promoted
hydrohalogenation
efficient
synthesis
aliphatic
chlorodifluoromethyl-,
bromodifluoromethyl-
iododifluoromethyl-containing
compounds
was
developed.
Particularly,
novel
provided
large-scale
access
various
iododifluoromethylated
high
value
synthetic
application.
Nature Communications,
Год журнала:
2023,
Номер
14(1)
Опубликована: Окт. 31, 2023
Transition
metal-catalyzed
carbonylative
reaction
with
CO
gas
are
among
the
central
task
in
organic
synthesis,
enabling
construction
of
highly
valuable
carbonyl
compound.
Here,
we
show
an
earth-abundant
nickel-catalyzed
three-component
tandem
acylzincation/cyclization
sequence
allene
and
alkylzinc
reagent
1
atm
under
mild
conditions.
This
protocol
is
featured
by
broad
functional
group
tolerance
high
selectivity,
providing
a
rapid
convenient
synthetic
method
for
diverse
fully
substituted
benzotropone
derivatives.
Mechanistic
studies
reveal
that
installation
cyano
tethered
to
moiety
enables
regio-
stereoselectivity
this
acylzincation
allene,
allowing
selective
formation
three
consecutive
C-C
bonds
efficient
manner.
ACS Catalysis,
Год журнала:
2024,
Номер
14(3), С. 1575 - 1583
Опубликована: Янв. 16, 2024
The
example
of
iron-catalyzed
reductive
fluoroalkylalkenylation
unactivated
alkenes
has
been
disclosed,
affording
the
stereodefined
homoallylic
fluoroalkanes
with
high
efficiency
and
regioselectivity.
This
three-component
cross-electrophile
coupling
features
directing
groups
free,
good
functional
group
tolerance,
broad
substrate
scope,
late-stage
difunctionalization
biorelevant
molecules.
Moreover,
this
protocol
sheds
light
on
distinct
reactivity
disparities
between
fluoroalkyl
nonfluoroalkyl
radicals
in
cross-coupling
reactions,
highlighting
unique
nature
iron/B2pin2
systems.
Organic Letters,
Год журнала:
2023,
Номер
25(45), С. 8110 - 8115
Опубликована: Ноя. 3, 2023
The
current
investigation
presents
an
innovative
palladium-catalyzed
asymmetric
carbonylative
Heck
esterification
method.
This
approach
facilitates
the
efficient
synthesis
of
various
chiral
γ-ketoacid
esters
by
utilizing
o-alkenyliodobenzenes
and
arylboronic
acids
as
primary
substrates.
reaction
achieves
creation
three
carbon–carbon
bonds,
two
carbon–oxygen
establishment
a
quaternary
carbon
center
within
single
step.
α-chiral
were
obtained
in
yields
ranging
from
good
to
high
yields,
displaying
enantiomeric
excesses
(ee's)
levels
up
92%
under
mild
conditions.
